Manufacture of esters and ethers of ethylidene glycol and of vinyl alcohol.



has been prepared by Neef (fl herraaentral p a without, other substance eapab n TED OFFICE:

FRITZ KLATTE, or scnwnnnnm on-rnn mnm; GERMANY, Assmnon TO 'cnnmscrm FABRIK GRIESHEIM-ELEKTBON, CORPORATION OF GERMANY,

OF FBANKFO RT-OK-THE-MAINQ GERMANY,- A.

MANUFACTURE or .nsprnns AND nurses or n'rnir mnnnn-omroon AND on nnconon,'-

No Drawing.

Specification a Letters Patent. 1 at t a 13, 1914,

Application filed August 26, 1913. Serial No. 786,760.

To all whom it may concern:

Be it known that-I, Fnrrz KLA'I'IE, a subject of the German Emperor, and resident of Schwanheim-on-the-Main, Germany, have invented certain new and useful Improve-u ments inthe Manufacture of Esters and is obtained by heating aoetaldehyde with aceticanhydrid ext-180 centigrade (Gouther, Annal 106,249), or in accordance with Wegscheider and Spath (Ohem. Centralblatt, 1910 I, 1421). whose, rocess consists in causing the formation 0 the ester at .a

lower temperature by the aid of a trace of sulfuric acid addedto the mixture of acetaldehyde and acetic anh drid, or in accordance with Wohland and egg, (Chem. 06%- tralblatt 1911 1,10) with a still better yield, by operating with an excess of acetaldehyde. Of theether-like compounds, for instance the 'aotalglycerin (.acetaldehyde glycerin, acetoglycero) 4 GHQ-OH Ebena.

Matt, 1904 II, 1201) with acetaldehyde at centigrade,

I have now found that bodies containing :hydroxyl and carboxyl groups combine with acetylene to a remarkable extent if the acetylene be passed through the said bodies when moderately heated and briskly stirred and when the operation is carried out in the presence of a suitable carrier such, for in-,

stance, as a salt of mercury (mercury-suffate, or phosphate, for example) with, or

e of actingas a carrier. In this way ethylidene esters or ethers, .are produced-mostly in quantitdtive I b heating glycerin em 160 to 200 .tively.

By the new reaction in accordance with. this invention it is-possible to produce a yield; these compounds being readily and smoothly obtained in accordance with the hitherto unknown reaction in accordance with the formula; 7

i cmcoo on-cn, cmcoo V QOHgCOOH CHECK In addition to this main reaction anotherv reaction (also hitherto unknown) takes place when acetylene reacts on acid namely, the

formation of vinyl esters by the reaction of ,one molecular proportion of acid with onemoleoule of acetylene:

.CHb-GOOH+QHECH+O1 C0O-CH-CH i v The quantities of the resulting vinyl esters differ with various aclds. For instance,

in the action of acetylene on tri-chlor-acetic acid, over 60 per cent. of the theoreticalyield of vinyl ester is obtained, as against a yield of vinyl acetate equal only up to about 5 per cent. of thetheoreticahhas hitherto been i usually obtained in the manufacture of ethylidene di-acetateL Under special conditions the yields of vinyl esters may be increased.

For instance on'passing acetylene throu h a mixture of formic acid and acetic am in the presence of mercury phosphate, equal parts of vinyl formate (boiling point 44 centigrade) and vinyl acetate. (boiling point- 72 centigrade) are formed.

The attachmentfof acetylene to alcohol s forming several acids is effected by two hydroxyl groups of one molecular proportion' reacting with one molecular -pro ortion of acetylene for instance, in the case 0 monochlorhydrin; EHQSI cruel H.011 onzcn no cn-om onion mo The process in accordance with thisin- :vention has the advantage over those already known that it is very economical as,

for'the purpose of obtaining'the esters the cheap carboxylic acids and. acetylene are.

used as initial materials instead of the costly 'a nhydrids and acetaldehyde respeclarge number of esters and ethe'rs some alegroup of-the alcohols, I mention ice especially the di-valent' glycols and glycerin and derivatives thereof, for instance,

mono-chlorhydrin and acetin, .in using which the reaction takes place readily and smoothly. But acetylene can also be at- ,tached to the monovalent alohols such for instance as, iso-amyl alcohol and iso-blltyl alcohol, ethylidene-di-isoamyl ether and 'ethylidene-di'-isobutyl ether being thereby obtained. "Of the aromatic'hydroxyl compounds, phenol and cresol-for instance when treated by the same process also absorb large amounts of acetylene; the products T resulting from the treatment being difficult can be varied b to obtain in a ure state. From the grou of acids the suitability of the react on wit the following acids has been investigated:

acetic acid, propionic acid, mono-, d1- and tri chlor-acetic acids, lactic acid and benzoic acid. In using benzoic acid,'it is necessary to use ,a solvent, acetic acid, for instance, being suitable. 'In addition to small amounts of ethylidene di-acetate, ethylidene acetate-benzoate and the, ethylidene-di-benzoate melting at 73 centi ade are obtained. That other" further bOdlGS containing hydroxyl groups react in the same manner with acetylene, is' exemplified by the pro-.

duction of the lacticacid nitrile compound.

In my'investi ations regardin the production of all t e aforesaid et ylidene and vinyl compounds, have found that" the initiation of the reaction is facilitated; that the reaction can be carried out at a lower 35 temperature and'that the proportion of the resulting ethylidene and vinyl compounds theaddition' of a small quantity of cats ytically acting substances, such for instance as mineral 'acid,- a sulfigiic acid, acid salt, or other analogous y. The following are examples of how the I invention can 'be performed butfI'do not f limit myself to these examples.

Example 1: 250 grams of anh drousacetic acid are mixed with 10 grams of mercury sulfate and ate temperature 1 of from to1l100,' centigrade dry acetylene is passedthrough' the mixture while it israpidly stirre The velocity, of the gas current is so adjusted that no unabsorbed gas leaves. the apparatus. When the combination'has pract cally ceased, the reaction product is 'subje'ctedto fractionaldistillation in 000140."

about-one cubic centimeter of concentrated sulfuric acid being added. At a tempera-' ture of from 60, to 7 0, centigrade thecom bination of the acetylene takes place. The

raw product is treated as descr bed in the preceding exam is by fractionalydistilla tion. The yiel of ethylidene propionate amounts to about from 60, to 70, per cent. of theoretical. j

Example 3: As described in the foregoing examples, acetylene is caused to react at'a temperature of from 60, to centigrade on 200 grams of molten trichlor-acetic acid 10 g'ramsof mercury sulfate-being added.

In a short time about 20" liters, or more, of

gas have combined. The reaction product is fractionatedz'n 'vacuo, the vinyl-trichloracetate first passing over. The oint oft-he latter is, at ordinary] atmosp eric pressure, about 149 .centigrade; The yield 'is from 60, to 7 0, per cent. of thetheoretical.

Example 4: Into 120 grains of iso-butylalcohol 'admixedjwith 12' grams. of mercury sulfate and 1 gram of anhydrous; sodium ,bisulfate, acetylene is introduced at a temperature of from to centigrade until the absorption of acetylene has ceased.

The reaction product is thereupon distilled off in vacuo and fractionated for'the purpose of purification of the ethylidene di-iso butyl ether obtained. The yield to 60 per cent. of the theoretical.

, 95 I is from 50,

Example 5: 100 grains of ethyleneglycol are mixed with 10 gramsof mercury sulfate;

and 0.2 cubic centimeters of concentrated sulfuric'acid andat a temperature of from"v 60, to 70, centigrade acetyleneis passed. i through .until the absorption of the S gas.

ceases. The resulting ethylene-ethylidene ether ,(boiling point 51 centi -ade)is distilled at ordinary pressure product. The yield is from cent. of the theoretical.

. y .105 9 the ;-.39. 9. p r 1 Example 6: 250fgrams of-i glycerin fare Y mixed with 10 grams of mercury sulfate and acetylene is. passed through at a temperature of from 60, to 70,centigrade as long as brisk combination ofthe gas takes place. The reaction mixture is preferably. allowed to settle and the supernatant clear. liquor is" fractionated in cacao; The yield of acetal glycerin is. almost quantitative.

7 Example 7: Into 200' grams of mono v chlorhydrin to which 10 grams of mercury sulfate have been added, acetylene is passedas above at a temperature of from 60,-to

-7.0,.centigrade. he reaction product,-.is'

allowed to settle and, from the supernatant a liqtuid, the .monorchlorhydrin etheris sepa ra ed; by fractionation .from thesmall" amount of unaltered" mono-chlo'rhydrin."

The-yield is almost theoretical; The ether boils at 148 centigrade.

It will a be seen from 'scription thatthe acetylene combines the above dewith the hydroxyl groups of the alcohols or carboxylic acids to form additional compounds, these compounds being esters when the acetylene combines with the hydroxyl group of the carboxylic acids, and

with acetylene on said compounds in the presence of a mercury salt.

2. The process of combining acetylene with organic compounds containing hydroxyl groups which comprises reacting with acetylene on said compounds while moderately heated and agitated and in the presence of a mercury salt.

3. The process of combining acetylene with organic compounds. containing hydroxyl groups which comprises reacting with acetylene on said compounds in the presence of a mercury salt and another substance capable of promoting the reaction. 4. The process of combining acetylene with organic compounds containing hydroxyl groups which comprises reacting with acetylene on said compounds while moderately heated and agitated and in the presence of a mercury salt and another substance capable of promoting the reaction.

5. The process of combining vacetylene with organic compounds containing hydroxyl groups whichcomprises reacting with acetylene on. said compounds in the presence of mercury sulfate.

6. The process of combining acetylene with organic compounds containing hydroxyl groups which comprises reacting with acetylene on said compounds while moderately heated and agitated andin the presence of mercury sulfate.

l. The process of forming esters of carboxylic ac1ds whlch comprises reacting with acetylene on said acids in the presence of,

a mercury salt.

S. The process of forming esters of carboxylic acids which comprises reacting with acetylene on said acids while moderately heated and agitated and in the presence of a mercury s'alt. c

9. The process of forming esters of carboxylic acids which comprises reacting with acetylene on said acids in the presenceof a mercury salt and another substance capable of promoting the reaction.

10. The process of forming esters of carboxy] ic acids which comprisesreacting with acetylene on said acids while moderately heated and agitated and in the presence of a mercury salt and another substance capable of promoting the reaction.

glycol hydroxyl groups.

11. The process of forming esters of carboxylic acids which comprises reacting with acetylene on said acids in the presence of mercury sulfate.

12. The process of forming esters of carboxylic acids which comprises reacting with acetylene on said acids while moderately heated and agitated and in the presence of mercury sulfate.

13. The process of producing derivatives of ethylidene glycol which comprises reacting with acetylene on organic compounds containing hydroxyl groups in the presence of a mercury salt, said compounds and acetylene being used in proportions to combine one molecule of acetylene with two hydroxyl groups of said compounds.

- 14. The process of producing derivatives of ethylidene glycol which comprises reacting with acetylene on organic compounds containing hydroxyl groups in the presence of a mercury salt, said compounds being moderately heated and agitated, and said compounds and acetylene being used in proportions to combine one molecule of acetylene with two hydroxyl groups of said compounds.

15. .The 'process of forming ethylidene derivatives of fatty acids which comprises reacting with acetylene on said 'acids in the presence of a mercury salt.

16. The process of forming ethylidene derivatives of fatty acids which comprises reacting with acetylene on said acids while moderately heated and agitated and in the presence of a mercury salt.

17. The process of forming ethylidene derivatives of fatty acids which comprises reacting with acetylene on said acids in the presence of a mercury salt and another substance capable of promoting the reaction.

18. The process of forming ethylidene derivatives of fatty acids which comprises reacting with acetylene on said acids while moderately heated and agitated and in the presence of .a mercury salt and another substance capable of promoting the reaction.

19. The process of forming ethylidene derivatives of fatty acids which comprises reacting with acetylene on said acids in th presence of mercury sulfate.

20. The process of forming ethylidene derivatives of fatty acids which comprises reacting with acetylene on said acids wlnle moderately heated and agitated and in the presence of mercury sulfate.

In testimony whereof I have signed my" name to this specification in the presence of two subscribing witnesses.-

' FRITZ KLATTE.

Witnesses: JEAN GRUND, ELSE Mamas. 

